CN103060840B - A kind of electrolytic seawater is produced clorox dynamic analog test method - Google Patents
A kind of electrolytic seawater is produced clorox dynamic analog test method Download PDFInfo
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- 239000013535 sea water Substances 0.000 title claims abstract description 60
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000010998 test method Methods 0.000 title claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000004458 analytical method Methods 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000000470 constituent Substances 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 238000007790 scraping Methods 0.000 claims description 6
- 238000009434 installation Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 29
- 238000004140 cleaning Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 235000021110 pickles Nutrition 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003619 algicide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to a kind of electrolytic seawater and produce clorox dynamic analog test method, the seawater that scene is obtained injects electrolyte water tank after filtering, be pumped into and in electrolytic cell, carried out electrolysis by the circulate electrolyte of electrolyte water tank lower part outlet, electrolytic cell water outlet comes back to carries out cyclic electrolysis in electrolyte water tank; By analyzing the impacts of definite seawater quality on electrode such as influent quality, available chlorine content, scale sample ingredient, for field apparatus type selecting and system provide technical support.
Description
Technical field
The present invention relates to a kind of electrolytic seawater and produce clorox dynamic analog test method.
Technical background
Along with maritime provinces expanding economy, coastal area starts extensive newly-built and extends coastal power plant to meet ever-increasing electricity needs, coastal power plant utilize seawater carry out Electrowinning clorox as the Processes and apparatus of circulating water sterilizing algicide started obtain application, but electrolytic seawater is produced clorox and is lacked dynamic analog test method, especially lacks the method that completes simulated test in laboratory. The electrolysis installation coming into operation is at present mostly taking seawater quality situation as foundation, and dependence experience designs. China coastline is vast, each coastal area seawater quality difference is larger, rely on the electrolysis installation of Experience Design to there will be unavoidably shorten electrode life, effective chlorine yields poorly, current efficiency is on the low side, the problems such as the problems such as electrolysis direct current power consumption is higher, even occur that short circuit of polar punctures, cell vessel high temperature melting. Therefore evaluate in the urgent need to the effect of seawater electrolysis being produced to clorox by simulated test, seawater quality and electrode body are affected and carry out analysis of experiments preparing chlorine by electrolysis, for the type selecting of electrolysis installation provides technical support.
Summary of the invention
Technical problem to be solved by this invention is for the problems referred to above, provides a kind of electrolytic seawater to produce clorox dynamic analog test method.
The present invention solves the problems of the technologies described above the technical scheme of taking:
A kind of electrolytic seawater is produced clorox dynamic analog test method, its step is as follows: the seawater that scene is obtained injects electrolyte water tank after filtering, be pumped into and in electrolytic cell, carry out electrolysis by the circulate electrolyte of electrolyte water tank lower part outlet, coutroi velocity is 0.5-5m3/h, voltage 5-10V, electrolytic cell water outlet comes back to carries out cyclic electrolysis in electrolyte water tank;
Wherein, start to analyze chlorine, calcium, magnesium, manganese and content of beary metal situation in seawater before electrolysis, in electrolytic process, observe the situation of change of Faradaic current, from starting, electrolysis measures the available chlorine content in seawater, and in electrolytic process results of regular determination electrolysis water outlet available chlorine content, the available chlorine content producing in electrolytic process is combined with Faradaic current and decomposition voltage and calculates current efficiency and direct current consumption;
After electrolysis finishes, the pole plate in electrolytic cell is taken out, scraping polar board surface dirt sample carries out constituent analysis, and gets electrolyte water tank bottom deposit and carry out constituent analysis, the fouling that analysis seawater produces in electrolytic process and the feature of deposited material;
After scraping dirt sample, pole plate is reinstalled to electrolytic cell, adopts the hydrochloric acid solution of 4%-8% to soak pole plate, soak after 1-2 hour, get soak and carry out constituent analysis, and it is emptying to remain soak, rinse electrolytic cell with clear water;
Determine the impact of seawater quality on electrode according to above-mentioned every analysis result, determine suitable electrolysis installation.
Described electrolyte water tank is cone bottom structure, and the deposit Direct precipitation producing in electrolytic process is at the cone end, and electrolyte circulating pump is connected with electrolyte water tank on cone top, the end, and the deposit producing before ensureing can not reenter in electrolytic cell with electrolyte; Electric heater unit and attemperating unit are housed in electrolyte water tank, control seawater electrolysis liquid water temperature at 0-50 DEG C.
The beneficial effect that the present invention adopts technique scheme to obtain is as follows:
(1) the invention provides the method for a kind of Fast Evaluation seawater electrolysis chlorine effect processed, by the impact of data analysis seawater quality on preparing chlorine by electrolysis efficiency such as the effective chlorine output, decomposition voltage and the Faradaic currents that obtain in electrolytic process, for field apparatus type selecting provides Data support.
(2) the inventive method adopts cyclic electrolysis mode, takes continuously a large amount of seawater test without scene that main equipment is placed on, and only adopts small simulation device can complete simulated test in laboratory; Cyclic electrolysis mode has also been accelerated the generation of incrustation, shorten test period, under laboratory condition, can realize rapid analysis scale sample ingredient and deposit composition, and then analyze the impact of seawater quality on pole plate, for field apparatus type selecting and system provide technical support.
Detailed description of the invention
Embodiment 1
1. dynamic analog test
Certain power plant's seawater (seawater quality situation is in table 1) is carried out to cyclic electrolysis test by this dynamic analog test method, and experimental condition is in table 2.
Table 1 seawater quality situation
Table 2 dynamic analog test condition
The effective chlorine output that test obtains and the current efficiency calculating and direct current consumption situation are in table 3.
Table 3 seawater electrolysis simulated test situation
The dirty sample situation of observing in test:
(1) new pole plate is in the time of initial launch, effective chlorine output is high, current efficiency is high, through after a period of time, surface forms one deck dirt will enter a steady-state operation state, i.e. the formation of dirt and a kind of poised state of peeling off, but this poised state is a kind of dynamic equilibrium, still have the slowly accumulation of dirt, just the speed of accumulation will be much smaller than the accumulative speed of new pole plate;
(2) pole plate incrustation is mainly on cathode plate, and plate does not have dirt substantially;
(3) dirty root and the pole plate both sides that are mainly distributed in cathode plate are the place that flow is less, and pole plate core dirt amount is less, and cathode plate influent side dirt is less, and water outlet side dirt is more;
(4) after seawater electrolysis, produced a certain amount of deposit, this should be in service in poised state, and the dirt of peeling off from polar board surface forms.
2. dirty sample and sediment analysis
Dirty sample and the water tank bottom deposit of scraping electrode surface have carried out constituent analysis, analysis result in table 4 to table 6.
Table 4 dynamic analog test seawater electrolysis dirt sample icp analysis
As can be seen from Table 4, polar board surface fouling after seawater electrolysis is all taking calcium magne-scale as main, sulfate scale does not almost have, should be taking carbonate scale and hydroxide magne-scale as main, have aluminium, manganese, titanium and the iron of minute quantity, and flow velocity lower place higher in negative electrode local pH value easily generates Mg (OH)2And CaCO3Precipitation, and there is not sulfate scale.
Dirty sample is also carried out to high temperature sintering test, found that in the dirty sample forming after seawater electrolysis and have 27% for organic matter.
Because layering has appearred in the deposit after seawater electrolysis, therefore two surface sediments are all carried out to constituent analysis, result is as follows.
Table 5 dynamic analog test seawater electrolysis upper layer sediment icp analysis
Table 6 dynamic analog test seawater electrolysis seabed sediment icp analysis
From table 5 and table 6, can find out, seawater electrolysis deposit is taking calcium magne-scale as main, and sulfate amount is little, and in deposit, taking magnesium salts as main, calcium salt is little.
3. dynamic analog test pole plate pickling situation analysis
3.1 pole plate acid cleaning process
According to above-mentioned analysis result, pole plate after seawater electrolysis is carried out to the test of hydrochloric acid soaking and washing, concentration of hydrochloric acid 5%, soak time 1 hour.
Found that according to the situation in acid cleaning process and pickling:
(1) in acid cleaning process, in electrolytic cell, occur a large amount of bubbles, illustrate that in polar board surface incrustation, carbonate composition is more, this and scale sample ingredient analysis result match;
(2) in acid cleaning process, the dirt of polar board surface constantly dissolves and comes off, and the organic matter that is attached to incrustation surface also comes off thereupon;
(3) hydrochloric acid reacts comparatively fast with incrustation, soaks after approximately 10 minutes, and polar board surface all cleans up substantially;
(4) polar board surface after pickling is clean, from the appearance there is no difference with new pole plate, and the incrustation that polar board surface is described is all carbonate scale and the hydroxide magne-scales that can be dissolved in hydrochloric acid;
3.2 pickle constituent analyses
For further confirming composition and the hydrochloric acid cleaning effect of polar board surface dirt, the pickle after the pickling of seawater electrolysis pole plate has been carried out to constituent analysis, analysis result is in table 7.
Table 7 dynamic analog test seawater electrolysis pole plate pickle icp analysis
As can be seen from Table 7, in pickle, taking calcium magnesium as main, sulfate is little, there is a small amount of manganese to be cleaned, this absolutely proves that incrustation after strong brine electrolysis, taking calcium carbonate and magnesium hydroxide as main, does not almost have sulfate, and these incrustation can be removed by hydrochloric acid cleaning completely.
Embodiment 2
1. dynamic analog test
In the present embodiment, seawater quality is in table 8, and dynamic analog test condition is identical with embodiment 1.
Table 8 seawater quality situation
The effective chlorine output that test obtains and the current efficiency calculating and direct current consumption situation are in table 9.
Table 9 seawater electrolysis simulated test situation
The dirty sample situation of observing in test:
(1) new pole plate is in the time of initial launch, effective chlorine output is high, current efficiency is high, through after a period of time, surface forms one deck dirt will enter a steady-state operation state, i.e. the formation of dirt and a kind of poised state of peeling off, but this poised state is a kind of dynamic equilibrium, still have the slowly accumulation of dirt, just the speed of accumulation will be much smaller than the accumulative speed of new pole plate;
(2) pole plate incrustation is mainly on cathode plate, and plate does not have dirt substantially;
(3) dirty root and the pole plate both sides that are mainly distributed in cathode plate are the place that flow is less, and pole plate core dirt amount is less, and cathode plate influent side dirt is less, and water outlet side dirt is more;
(4) after seawater electrolysis, produced a certain amount of deposit, this should be in service in poised state, and the dirt of peeling off from polar board surface forms.
2. dirty sample and sediment analysis
Dirty sample and the water tank bottom deposit of scraping electrode surface have carried out constituent analysis, and analysis result is in table 10 and table 11.
Table 10 dynamic analog test seawater electrolysis dirt sample icp analysis
As can be seen from Table 10, polar board surface fouling after seawater electrolysis is all taking calcium magne-scale as main, sulfate scale does not almost have, should be taking carbonate scale and hydroxide magne-scale as main, have aluminium, manganese, titanium and the iron of minute quantity, and flow velocity lower place higher in negative electrode local pH value easily generates Mg (OH)2And CaCO3Precipitation, and there is not sulfate scale.
Dirty sample is also carried out to high temperature sintering test, found that in the dirty sample forming after seawater electrolysis and have 24% for organic matter.
Deposit after seawater electrolysis has been carried out to constituent analysis, and result is as follows.
Table 11 dynamic analog test seawater electrolysis deposit icp analysis
As can be seen from Table 11, seawater electrolysis deposit is taking calcium magne-scale as main, and sulfate amount is little, and in deposit, taking magnesium salts as main, calcium salt is little.
3. dynamic analog test pole plate pickling situation analysis
3.1 pole plate acid cleaning process
According to above-mentioned analysis result, pole plate after seawater electrolysis is carried out to the test of hydrochloric acid soaking and washing, concentration of hydrochloric acid 5%, soak time 1 hour.
Found that according to the situation in acid cleaning process and pickling:
(1) in acid cleaning process, in electrolytic cell, occur a large amount of bubbles, illustrate that in polar board surface incrustation, carbonate composition is more, this and scale sample ingredient analysis result match;
(2) in acid cleaning process, the dirt of polar board surface constantly dissolves and comes off, and the organic matter that is attached to incrustation surface also comes off thereupon;
(3) hydrochloric acid reacts comparatively fast with incrustation, soaks after approximately 10 minutes, and polar board surface all cleans up substantially;
(4) polar board surface after pickling is clean, from the appearance there is no difference with new pole plate, and the incrustation that polar board surface is described is all carbonate scale and the hydroxide magne-scales that can be dissolved in hydrochloric acid;
3.2 pickle constituent analyses
For further confirming composition and the hydrochloric acid cleaning effect of polar board surface dirt, the pickle after the pickling of seawater electrolysis pole plate has been carried out to constituent analysis, analysis result is in table 12.
Table 12 dynamic analog test seawater electrolysis pole plate pickle icp analysis
As can be seen from Table 12, in pickle, taking calcium magnesium as main, sulfate is little, there is a small amount of manganese to be cleaned, this absolutely proves that incrustation after strong brine electrolysis, taking calcium carbonate and magnesium hydroxide as main, does not almost have sulfate, and these incrustation can be removed by hydrochloric acid cleaning completely.
Claims (2)
1. an electrolytic seawater is produced clorox dynamic analog test method, it is characterized in that its step is as follows: the seawater that scene is obtained injects electrolyte water tank after filtering, be pumped into and in electrolytic cell, carry out electrolysis by the circulate electrolyte of electrolyte water tank lower part outlet, coutroi velocity is 0.5-5m3/h, voltage 5-10V, electrolytic cell water outlet comes back to carries out cyclic electrolysis in electrolyte water tank;
Wherein, start to analyze chlorine, calcium, magnesium, manganese and content of beary metal situation in seawater before electrolysis, in electrolytic process, observe the situation of change of Faradaic current, from starting, electrolysis measures the available chlorine content in seawater, and in electrolytic process results of regular determination electrolysis water outlet available chlorine content, the available chlorine content producing in electrolytic process is combined with Faradaic current and decomposition voltage and calculates current efficiency and direct current consumption;
After electrolysis finishes, the pole plate in electrolytic cell is taken out, scraping polar board surface dirt sample carries out constituent analysis, and gets electrolyte water tank bottom deposit and carry out constituent analysis, the fouling that analysis seawater produces in electrolytic process and the feature of deposited material;
After scraping dirt sample, pole plate is reinstalled to electrolytic cell, adopts the hydrochloric acid solution of 4%-8% to soak pole plate, soak after 1-2 hour, get soak and carry out constituent analysis, and it is emptying to remain soak, rinse electrolytic cell with clear water;
Determine the impact of seawater quality on electrode according to above-mentioned every analysis result, determine suitable electrolysis installation.
2. a kind of electrolytic seawater according to claim 1 is produced clorox dynamic analog test method, it is characterized in that described electrolyte water tank is for cone bottom structure, the deposit Direct precipitation producing in electrolytic process is at the cone end, electrolyte circulating pump is connected with electrolyte water tank on cone top, the end, and the deposit producing before ensureing can not reenter in electrolytic cell with electrolyte; Electric heater unit and attemperating unit are housed in electrolyte water tank, control seawater electrolysis liquid water temperature at 0-50 DEG C.
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| CN108455767B (en) * | 2018-02-26 | 2021-08-10 | 洪先正 | Electrolysis device |
| CN108950590A (en) * | 2018-07-11 | 2018-12-07 | 青海盐湖工业股份有限公司 | A kind of system and method for primary brine quality in control chlor-alkali production |
| CN109234763B (en) * | 2018-11-20 | 2023-11-10 | 青岛双瑞海洋环境工程股份有限公司 | Full-automatic test system for performance of sodium hypochlorite device prepared by electrolysis of saline solution |
| CN110042417A (en) * | 2019-05-21 | 2019-07-23 | 中国水利水电科学研究院 | A kind of method and device of electrolytic seawater production javelle water |
| CN110983365A (en) * | 2019-11-22 | 2020-04-10 | 首钢京唐钢铁联合有限责任公司 | System and method for preparing chlorine by electrolyzing seawater |
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